CN114163143A - Halide nanocrystalline dispersion glass and application thereof - Google Patents

Halide nanocrystalline dispersion glass and application thereof Download PDF

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CN114163143A
CN114163143A CN202111557316.7A CN202111557316A CN114163143A CN 114163143 A CN114163143 A CN 114163143A CN 202111557316 A CN202111557316 A CN 202111557316A CN 114163143 A CN114163143 A CN 114163143A
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glass
ion exchange
halide
nanocrystals
molten salt
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CN114163143B (en
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刘超
周耀
叶英
李凯
张玉东
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Wuhan University of Technology WUT
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C03C3/074—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc
    • H—ELECTRICITY
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials

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Abstract

The invention relates to halide nanocrystalline dispersion glass and application thereof. The surface layer of the dispersion glass is a Cs ion exchange layer, the halide nanocrystals are distributed in the Cs ion exchange layer, and the halide nanocrystals comprise CsPbX3、Cs4PbX6CsX or KX, wherein X is one or the combination of more than two of Cl, Br and I. The invention adopts cation exchange to realize the controllable preparation of halide nanocrystals and cesium-lead halide perovskite nanocrystals in a certain depth range on the surface layer of the glass, and combines the glass composition design and the cation exchangeThe process adjustment is changed, and the controllable preparation of various cesium-lead halogen perovskite nanocrystals and halide nanocrystals in the surface layer of the glass can be realized. The cesium-lead-halogen perovskite nanocrystalline dispersion glass provided by the invention can be used for preparing cesium-lead-halogen perovskite nanocrystalline with controllable depth range, controllable crystal variety and adjustable absorption and light-emitting wave band in the surface layer of glass, and has application value in the fields of illumination, backlight source, information display and the like.

Description

Halide nanocrystalline dispersion glass and application thereof
Technical Field
The invention belongs to the field of nanocrystalline materials and preparation methods thereof, and particularly relates to halide nanocrystalline dispersion glass and application thereof.
Background
Halide nanocrystals, especially cesium-lead halide perovskite nanocrystals are an important luminescent material and have important application values in the fields of illumination, backlight sources, information display and the like. But the stability of the cesium-lead halide perovskite nano crystal is poor, so that the wide application of the cesium-lead halide perovskite nano crystal is restricted. It is usually necessary to improve the stability by means of coating or the like or by dispersing into a stable material. The glass material has good stability, and the cesium-lead halogen perovskite nanocrystalline is dispersed in the glass material, so that the influence of the external environment on the stability of the cesium-lead halogen perovskite nanocrystalline can be isolated. Although the preparation process of the cesium-lead halogen perovskite nanocrystalline dispersion glass is mature, the cesium-lead halogen perovskite nanocrystalline dispersion glass is generally prepared in a melting-forming-heat treatment mode, and formed cesium-lead halogen perovskite nanocrystalline is randomly distributed in a glass matrix, so that a photoelectric functional device is difficult to prepare. The cesium-lead-halogen perovskite nanocrystalline dispersion glass prepared by the method has the advantages that the density of cesium-lead-halogen perovskite nanocrystals formed in the glass is low, the cesium-lead-halogen perovskite nanocrystals are difficult to effectively absorb a specific light source, the serious self-absorption phenomenon is easy to cause, and the overall efficiency of a photoelectric device is reduced. Therefore, the development of a novel preparation method of cesium-lead halogen perovskite nanocrystalline dispersion glass is urgently needed.
Disclosure of Invention
The invention provides halide nanocrystalline dispersion glass and application thereof for solving the technical problems. The method adopts cation exchange to realize the controllable preparation of halide nanocrystals and cesium-lead perovskite nanocrystals within a certain depth range on the surface layer of the glass, and combines the composition design of the glass and the adjustment of the cation exchange process to realize the controllable preparation of various cesium-lead perovskite nanocrystals and halide nanocrystals in the surface layer of the glass. The cesium-lead-halogen perovskite nanocrystalline dispersion glass provided by the invention can be used for preparing cesium-lead-halogen perovskite nanocrystalline with controllable depth range, controllable crystal variety and adjustable absorption and light-emitting wave band in the surface layer of glass, and has application value in the fields of illumination, backlight source, information display and the like.
The purpose of the invention is realized by the following technical scheme:
the surface layer of the dispersion glass is a Cs ion exchange layer, halide nanocrystals are distributed in the Cs ion exchange layer, and the halide nanocrystals comprise CsPbX3、Cs4PbX6CsX or KX, wherein X is one or the combination of more than two of Cl, Br and I.
Preferably, the depth of the ion exchange layer is 0-80 μm.
Preferably, the network former of the glass is SiO2、B2O3、GeO2、TeO2Or P2O5One or a combination of two or more of them.
Preferably, the network former of the glass is SiO2、B2O3Or P2O5One or a combination of two or more of them.
Preferably, the network former of the glass is SiO2Or SiO2And B2O3Combinations of (a) and (b).
Preferably, the composition of the glass comprises, in mole percent: 1-8% of PbO and 3-16% of AX, wherein A is any one or the combination of more than two of Li, Na or K, and X is one or the combination of more than two of Cl, Br or I.
Preferably, the halide nanocrystal CsPbX3The specific kind of (b) corresponds to the halogen element contained in the glass.
Preferably, the Cs ion exchange layer is used for exchanging alkali metal cations in the glass with cesium ions in the cesium-containing molten salt; the cesium-containing molten salt is Cs molten salt, Cs/K mixed molten salt, Cs/Na mixed molten salt or Cs/K/Na mixed molten salt.
Preferably, the ion exchange temperature is 420-510 ℃,
Preferably, when the molar ratio of Cs/K in the molten salt is greater than or equal to 1, the nanocrystal is Cs4PbX6And/or CsPbX3A nanocrystal; when the molar ratio of Cs/K in the molten salt is less than 1, the nanocrystal is CsPbX3Nanocrystals and KX nanocrystals.
Preferably, CsPbX in the dispersed glass3The absorption band and the luminescence band of the nanocrystal can be regulated and controlled within the range of 450-700 nm.
The halide nanocrystalline dispersion glass is applied to the fields of light-emitting components, light source devices, spectrum conversion devices or light-emitting indicating equipment.
The invention has the following beneficial effects:
1) the cation exchange method provided by the invention prepares halide nanocrystals on the surface layer of glass, in particular CsPbX with luminescence property3Nanocrystalline, compared with the conventional melting heat treatment method for preparing CsPbX3For the nanocrystalline, the consumption of high-cost Cs ions can be reduced, the content of halogen elements in glass can be increased, and the method has very important significance for preparing the cesium-lead halogen perovskite nanocrystalline with high luminescence property.
2) The halide nanocrystal prepared by the invention, in particular to CsPbX with luminescence property3The nanocrystals are only distributed on the surface layer of the ion exchange glass, so that the two-dimensional distribution regulation of the halide nanocrystals in the glass is realized, the problem that the halide nanocrystals prepared in the conventional melting heat treatment method are randomly distributed in a three-dimensional space is solved, and the application of the halide nanocrystals based on film display, luminescence, backlight source and the like has higher practical value. Meanwhile, the halide nanocrystalline dispersion glass with two-dimensional distribution also reduces the consumption of the glass, and has important significance for reducing the use amount of the glass and the weight of related devices.
3) The cation exchange method provided by the invention can be used for preparing halide nanocrystals in glass, can realize the controllable preparation of various halide nanocrystals in glass through simple adjustment of an ion exchange process, and provides a new idea for the design and preparation of novel halide nanocrystal dispersion glass.
4) The halide nanocrystalline dispersion glass prepared by the invention can avoid the self-absorption phenomenon caused by the traditional melting heat treatment method, and improve the overall optical efficiency of the photoelectric device. Meanwhile, compared with the glass prepared by the traditional melting heat treatment method, the glass prepared by ion exchange has higher mechanical strength.
In conclusion, the cation exchange method provided by the invention is used for preparing the halide nanocrystal, in particular to CsPbX with the luminescence property3The nanocrystalline dispersion glass can be conveniently combined with a microstructure array processing method and technology based on ion exchange to realize the preparation of a halide array with a luminous property in the glass, and has important application value in the novel display fields of Micro-LEDs, Mini-LEDs, backlight sources and the like.
Drawings
In the following figures, AP represents the original glass sample, i.e., the glass sample obtained by melt-forming without ion-exchange; in the following drawings, in the XXX-XX expression, the first three bits XXX represent the ion exchange temperature (. degree. C.) and the number after "-" represents the time (h).
FIG. 1 is a graph showing the absorption spectrum of a glass sample after ion exchange of AP in example 1.
FIG. 2 is a graph showing the luminescence spectrum of a glass sample after ion-exchange of AP in example 1.
FIG. 3 is a Cs and K distribution diagram of 500 deg.C/15 h ion-exchanged glass sample in example 1.
FIG. 4 is a high resolution TEM image of a single nanocrystal in a 500 deg.C/15 h sample of ion exchanged glass from example 1.
FIG. 5 is a transmission electron micrograph of the surface layer portion of the 500 ℃/15h ion-exchanged glass sample of example 1.
FIG. 6 is a graph showing the density change of nanocrystals in the surface layer of 500 deg.C/15 h ion-exchanged glass in example 1.
FIG. 7 is a graph showing the absorption spectra of the glass as-received in example 2 and after ion exchange treatment under different temperature and time conditions.
FIG. 8 is a graph showing luminescence spectra of the glass as-received in example 2 and after ion exchange treatment under different temperature and time conditions.
FIG. 9 is a chart of the optical spectrum of the glass as-received in example 5 after it was subjected to ion exchange conditions at different temperatures and times.
FIG. 10 is a graph of the reported optical spectra of the glass pristine sample of example 6 and after ion exchange conditions at different temperatures and times.
FIG. 11 is a chart of the optical spectrum of the glass as-received in example 8 after it was subjected to ion exchange conditions at different temperatures and times.
FIG. 12 is a graph showing the absorption spectra of the glass as-received in example 21 after treatment with ion exchange conditions at 460 ℃ for various times.
FIG. 13 is an absorption spectrum of the glass as it is in example 21 after treatment at 480 ℃ for various time under ion exchange conditions.
FIG. 14 is a graph showing fluorescence spectra of the glass as it is in example 21 after being treated with ion exchange conditions at 460 ℃ for various times.
FIG. 15 is a graph showing fluorescence spectra of the glass original sample of example 21 after treatment with ion exchange conditions at 480 ℃ for various periods of time.
FIG. 16 is an XRD pattern of the glass pristine sample of example 21 after treatment with 460 ℃ ion exchange conditions for various periods of time.
FIG. 17 is an XRD pattern of the glass pristine sample of example 21 after treatment with ion exchange conditions at 480 ℃ for various times.
FIG. 18 is a graph showing the absorption spectra of the glass as-received in example 22 after treatment with ion exchange conditions at 460 ℃ for various times.
FIG. 19 is an absorption spectrum of a glass as it is in example 22 after treatment at 480 ℃ for various time under ion exchange conditions.
FIG. 20 is a graph showing fluorescence spectra of a glass as it is in example 22 after being treated with ion exchange conditions at 460 ℃ for various times.
FIG. 21 is a graph showing fluorescence spectra of a glass as it is in example 22 after being treated with ion exchange conditions at 480 ℃ for various periods of time.
FIG. 22 is an XRD pattern of the glass pristine sample of example 22 after treatment with 460 ℃ ion exchange conditions for various periods of time.
FIG. 23 is an XRD pattern of the glass pristine sample of example 22 after treatment with ion exchange conditions at 480 ℃ for various times.
FIG. 24 is a graph showing the absorption spectra of the glass as-received in example 23 after treatment with ion exchange conditions at 460 ℃ for various times.
FIG. 25 is a graph showing the absorption spectra of the glass as-received in example 23 after treatment with ion exchange conditions at 480 ℃ for various periods of time.
FIG. 26 is a graph showing fluorescence spectra of a glass as it is in example 23 after treatment with ion exchange conditions at 460 ℃ for various times.
FIG. 27 is a graph showing fluorescence spectra of a glass original sample obtained in example 23 after treatment under ion exchange conditions at 480 ℃ for various periods of time.
FIG. 28 is an XRD pattern of the glass pristine sample of example 23 after treatment with ion exchange conditions at 460 ℃ and 480 ℃ for various periods of time.
FIG. 29 is a graph showing the absorption spectra of the glass as-received in example 24 after treatment with ion exchange conditions at 460 ℃ for various times.
FIG. 30 is a graph showing the absorption spectra of the glass as-received in example 24 after treatment with ion exchange conditions at 480 ℃ for various periods of time.
FIG. 31 is a graph showing fluorescence spectra of the glass as-received in example 24 after treatment with ion exchange conditions at 460 ℃ for various times.
FIG. 32 is a graph showing fluorescence spectra of the glass original sample of example 24 after treatment with ion exchange conditions at 480 ℃ for various periods of time.
FIG. 33 is an XRD pattern of the glass pristine sample of example 24 after treatment with 460 ℃ ion exchange conditions for different periods of time.
FIG. 34 is an XRD pattern of the glass pristine sample of example 24 after treatment with ion exchange conditions at 480 ℃ for various times.
FIG. 35 is a graph showing the absorption spectra of the glass as-received in example 25 after treatment with ion exchange conditions at 460 ℃ for various times.
FIG. 36 is a graph showing the absorption spectra of the glass as-received in example 25 after treatment with ion exchange conditions at 480 ℃ for various periods of time.
FIG. 37 is a graph showing fluorescence spectra of a glass as it is in example 25 after treatment with ion exchange conditions at 460 ℃ for various times.
FIG. 38 is a graph showing fluorescence spectra of a glass original sample obtained in example 25 after treatment under ion exchange conditions at 480 ℃ for various periods of time.
FIG. 39 is an XRD pattern of the glass pristine sample of example 25 after treatment with ion exchange conditions at 460 ℃ and 480 ℃ for various periods of time.
FIG. 40 is a graph showing the absorption spectra of the glass as-received in example 26 after treatment with ion exchange conditions at 460 ℃ and 480 ℃ for various periods of time.
FIG. 41 is a graph showing fluorescence spectra of a glass as a starting material in example 26 after treatment with ion exchange conditions at 460 ℃ and 480 ℃ for various periods of time.
FIG. 42 is an XRD pattern of the glass pristine sample of example 26 after treatment with ion exchange conditions at 460 ℃ and 480 ℃ for various periods of time.
Detailed Description
The invention is further illustrated by the following examples.
In the halide nanocrystal, CsPbX3The nanocrystal is a nanocrystal having a luminescent characteristic in a visible light band. Examples 1 to 8 for CsPbX having luminescence characteristics in the visible light band3The composition, absorption and luminescence band regulation of the nanocrystals are explained.
Example 1
Weighing the following raw materials in percentage by mole: SiO 22:35％，B2O3:35％，ZnO:5％，CaO:5％，PbO:2％，Na23 percent of O and 15 percent of KBr. After being mixed evenly, the mixture is melted for 20min at 1230 ℃, and then is rapidly cooled, formed and annealed to obtain the completely transparent glass. Cutting and polishing the original glass, and then performing CsNO at 480-510 DEG C3Ion exchange is carried out in the molten salt to obtain CsPbBr3Nanocrystalline dispersed transparent glass.
FIG. 1 is an absorption spectrum of a glass sample after AP and ion exchange. As can be seen from FIG. 1, as the ion exchange temperature increases or the time increases, the position of the absorption peak shoulder in the spectrum gradually shifts from 481nm to 505 nm; indicating that CsPbBr was formed in the glass after ion exchange3Nanocrystals, and the nanocrystals gradually grow larger. In the glass sample in FIG. 1, under the excitation of 360nm light, visible light is observed in the sample after AP and ion exchange. AP sample calendarIon exchange shows that there is no CsPbBr in AP3The nanocrystal presents wide-spectrum luminescence of 380-600nm waveband, and the luminescence is from Pb related to Br2+The electron transition of ion 6s6p → 6s 2. The glass sample exchanged for 10 hours (480-10, the same below) at 480 ℃ also showed broad-spectrum luminescence in the 380-600nm band, which indicates that CsPbBr is formed in the glass under the exchange condition3The content of the nano-crystal is low, and the luminescence of the glass is still Pb related to Br2+Ion luminescence is dominant. In a glass sample exchanged for 10 hours at 490 ℃, the wide-spectrum luminescence of 380-600nm waveband and 497nm narrow-band luminescence are presented; with the further increase of the ion exchange temperature or the prolonging of the time, the glass sample after the ion exchange shows narrow-band luminescence, and the central wavelength of the narrow-band luminescence gradually moves towards the long wave direction. This is consistent with the results presented in FIG. 1, illustrating the formation of CsPbBr in the ion-exchanged glass3The nanocrystals gradually became larger. The above results show that, in the case of a constant molten salt, the size of the nanocrystals formed in the glass surface layer can be controlled by adjusting the temperature or time of ion exchange.
To further clarify the effect of ion exchange in the present invention, the distribution of Cs ions in the surface layer of the ion-exchanged glass was analyzed by Electron Probe Microscopy (EPMA), and the results are shown in FIG. 3. The AP glass contains K ions and Na ions, but the difference between the radiuses of the K ions and the Cs ions is small, so that the Cs-K ion exchange is easier to perform, and the distribution condition of the Cs and the K ions after ion exchange is reflected in the EPMA analysis result. The results show that after ion exchange, the Cs content (or concentration, the same applies hereinafter) gradually decreases from the glass surface toward the glass interior, while the K content gradually increases from the glass surface toward the glass interior until the average concentration of K ions in the glass is reached. As a result, the Cs ion distribution depth after ion exchange was 5.1 μm; the Cs ions partially exchanged into the glass form CsPbBr with Pb and Br contained in the glass3And (4) nanocrystals.
FIG. 4 shows CsNO3High resolution transmission electron microscopy of individual nanocrystals in the surface layer in a glass sample exchanged at 500 ℃ for 15 hours in molten salt. The lattice fringes of the nanocrystals shown in the figure correspond to the orthorhombic structure CsPbBr3The (121) crystal face (JCPDS card number: 74-2251, space group pmnb) of (A) further proves that the nanocrystal formed in the glass after ion exchange is CsPbBr3And (4) nanocrystals.
FIG. 5 shows CsNO3High resolution transmission electron microscopy of the surface layer in a glass sample exchanged in molten salt at 500 ℃ for 15 hours. The rightmost side of the figure is the glass surface, the strip-shaped rectangular frame in the figure is vertical to the glass surface, and the strip-shaped rectangle is further divided into a plurality of small rectangular frames with the width of 100 nm. As can be seen from FIG. 5, CsPbBr formed in the surface layer of the glass after ion exchange3The density of the nano-crystals gradually decreases from the surface of the glass to the interior of the glass, and the distribution range is about 2.5 mu m and is basically half of the diffusion depth of Cs ions. FIG. 6 shows the statistics of CsPbBr in each rectangular box with a width of 100nm3The number of nanocrystals. The results in fig. 6 also show that the density of nanocrystals formed in the surface layer of the glass gradually decreased after ion exchange, which is consistent with the distribution of the Cs content in the surface layer of the ion-exchanged glass in fig. 3. Comparison of the results in fig. 3 and 6 shows that it is difficult to form halide nanocrystals, especially cesium lead halide nanocrystals, in the glass when the Cs ion concentration in the surface glass is reduced to a certain extent. Therefore, the concentration distribution of the Cs concentration in the glass surface layer can be further regulated and controlled by regulating the concentration of the Cs ions in the molten salt, the ion exchange time, the temperature and the like, so that the distribution of the halide nanocrystals or the cesium lead halide nanocrystals in the glass surface layer after ion exchange can be regulated.
Example 2
The glass of this example had a composition (in mole percent) of SiO2:35％，B2O3:35％，ZnO:5％，CaO:5％，PbO:2％，Na23 percent of O, 3.75 percent of KCl and 11.25 percent of KBr. The glass preparation and ion exchange methods and conditions were the same as in example 1. The difference between this example and example 1 is that KCl is introduced into the glass composition, and the ratio of the contents of KCl and KBr is 1: 3. FIGS. 7 and 8 show the CsNO of the sample of this embodiment3And (3) an absorption spectrum of a glass sample obtained after ion exchange in molten salt. As the ion exchange temperature increased, the absorption peak shoulder of the ion exchange sample gradually red-shifted from 488nm to 501nm (FIG. 7), and the luminescence peak red-shifted from 488nm to 508nm (FIG. 8).
Example 3
The glass of this example had a composition (in mole percent) of SiO2:35％，B2O3:35％，ZnO:5％，CaO:5％，PbO:2％，Na23 percent of O, 7.5 percent of KCl and 7.5 percent of KBr. The difference between this example and example 2 is that the ratio of KCl to KBr content is 1: 1. The absorption peak shoulders of the ion exchange glass samples are located at 467nm (480 ℃/10h, the ion exchange temperature and time are shown in brackets, the same is shown below), 472nm (500 ℃/5h), 474nm (500 ℃/10h), 475nm (500 ℃/15h) and 480nm (510 ℃/10h), and the corresponding luminescence peaks of the samples are located at 481nm (480 ℃/10h), 484nm (500 ℃/5h), 486nm (500 ℃/10h), 487nm (500 ℃/15h) and 489nm (510 ℃/10 h).
Example 4
The glass of this example had a composition (in mole percent) of SiO2:35％，B2O3:35％，ZnO:5％，CaO:5％，PbO:2％，Na23 percent of O, 11.25 percent of KCl and 3.75 percent of KBr. The difference between this example and example 3 is that the ratio of KCl to KBr content is 3: 1. The absorption peaks of the ion-exchange glass samples are located at 440nm (490 ℃/10h), 441nm (500 ℃/10h) and 444nm (510 ℃/10h), and the luminescence peaks are located at 448nm (480 ℃/10h), 450nm (490 ℃/10h), 450nm (500 ℃/10h) and 453nm (510 ℃/10 h).
Examples 2-4 demonstrate that the composition and forbidden bandwidth of halide nanocrystals formed in glass can be adjusted by adjusting the relative content of Cl and Br in the glass in combination with the adjustment and control of ion exchange temperature and time, and the absorption peak and luminescence peak bands of the halide nanocrystals formed in glass can be effectively adjusted. Examples 2-4 illustrate that the nanocrystals formed in the above glasses are CsPb (Cl/Br)3And (4) nanocrystals.
Example 5
The glass of this example had a composition (in mole percent) of SiO2:30％，B2O3:35％，ZnO:8％，CaO:5％，PbO:4％，K 24 percent of O and 16 percent of KI. The glass preparation and ion exchange methods and conditions were the same as in example 1. The biggest difference between the present embodiment and the above embodiments is that the halogen introduced into the glass is an I element. As shown in FIG. 9, the AP glass sample still appeared in the present exampleShows wide-spectrum luminescence related to Pb ions, but after the glass sample is subjected to ion exchange under the conditions of 480 ℃/10h, 500 ℃/5h and 500 ℃/10h, the central wavelengths of luminescence peaks of the glass sample are respectively positioned at 660nm, 668nm and 678 nm. The luminescence of the above examples in the red band illustrates that the halide nanocrystals formed in the surface layer of the glass after ion exchange are CsPbI3Perovskite nanocrystals. With reference to examples 1 to 4, the kind of halide nanocrystals formed in the surface layer of the glass can be controlled by adjusting the kind of halogen element in the glass.
Example 6
The glass of this example had a composition (in mole percent) of SiO2:30％，B2O3:35％，ZnO:8％，CaO:5％，PbO:2％，K 24% of O, KBr: 4 percent and KI 12 percent. The glass preparation and ion exchange methods and conditions were the same as in example 1. The difference between this example and the above example is that the present example introduces Br and I elements at the same time, and the Br/I ratio is 1: 3. FIG. 10 is a graph showing the luminescence spectra of the AP sample and the ion-exchanged AP sample of this example. The AP sample also showed broad-spectrum luminescence associated with Pb ions, and the luminescence peaks of the halide nanocrystals formed in the glass after ion exchange were located at 634nm (500 ℃/5h), 647nm (480 ℃/10h), 649nm (500 ℃/10h) and 657nm (500 ℃/15 h).
Example 7
The glass of this example had a composition (in mole percent) of SiO2:30％，B2O3:35％，ZnO:8％，CaO:5％，PbO:2％，K 24% of O, KBr: 8 percent and 8 percent of KI. The glass preparation and ion exchange methods and conditions were the same as in example 1. The difference between this example and example 6 is that the Br/I ratio in this example is 1: 1. The luminescence peaks of the halide nanocrystals formed in the glass after ion exchange are located at 591nm (500 ℃/5h), 601nm (500 ℃/10h) and 618nm (480 ℃/10 h).
Example 8
The glass of this example had a composition (in mole percent) of SiO2:30％，B2O3:35％，ZnO:8％，CaO:5％，PbO:2％，K 24% of O, KBr: 12 percent and KI:4 percent. Glass preparation and ion exchange process and conditionsThe same applies to example 1. The difference between this example and examples 6 and 7 is that the Br/I ratio in this example is 3: 1. The luminescence peak of the halide nanocrystals formed in the glass after ion exchange is adjustable within the 513-537nm band (FIG. 11).
Examples 6 to 8 show that the type and particle size of halide nanocrystals formed in the surface layer of glass can be adjusted by adjusting the content of Br and I elements in the glass, and combining the processes of ion exchange temperature and time. In comparison with examples 1-5, the halide nanocrystals formed in examples 6-8 were CsPb (Br/I)3And (4) nanocrystals.
The above examples illustrate that CsPbX formed in the surface layer of glass can be controlled by adjusting the type and amount of halogen in the glass, in combination with adjusting the ion exchange temperature and time3The composition, absorption and luminescence wave bands of the nanocrystalline are regulated and controlled. The results of example 1 show that the depth of the Cs ion layer in the glass surface layer determines the depth of distribution of the halide nanocrystals in the glass surface layer. Aiming at the situation, the invention also provides a method for regulating and controlling the exchange depth of Cs ions in glass. In order to more simply describe the method for regulating the Cs ion exchange depth in the present invention, only the composition containing Br is taken as an example in the present invention. However, it should be noted that the Cs ion exchange depth control method of the present invention has similar effects for other halide nanocrystals involved in the present invention. The glass compositions of the present examples are shown in Table 1.
Table 1, examples 9-20 glass compositions and Cs ion exchange layer depth. The cesium-containing molten salt used in examples 9 to 20 was CsNO3Molten salt, using ion exchange conditions of 500 ℃/10 h. The Cs ion diffusion depth was determined using Electron Probe Microscopy (EPMA) method.
Figure BDA0003419417650000091
Figure BDA0003419417650000101
Example 9 in comparison with example 10High glass medium K2O content and simultaneously reduce SiO in the glass2In the CsNO content3After 10h of exchange in the molten salt at 500 ℃, the depth of the Cs ion exchange layer in the glass of example 9 was 9 μm, and the depth of the Cs ion exchange layer in the glass of example 10 was 34 μm.
Examples 11 and 12 improved Al content in glass as compared with example 132O3Content while reducing SiO in the glass2In the CsNO content3After 10 hours of exchange in the molten salt at 500 ℃, the depth of the Cs ion exchange layer in the glass of example 11 was 23.4 μm, the depth of the Cs ion exchange layer in the glass of example 12 was 31 μm, and the depth of the Cs ion exchange layer in the glass of example 13 was 41 μm.
Example 14 in comparison with example 13, the amount of B in the glass was increased2O3The content is reduced, and the ZnO content is reduced, so that the depth of a Cs ion exchange layer is not greatly influenced.
Example 15 in comparison with example 13, the content of alkaline earth metal oxide (e.g., BaO) in the glass was increased and SiO was reduced2In the CsNO content3After 10h of exchange in the molten salt at 500 ℃, the Cs ion exchange layer depth was reduced to 35 μm.
Example 16 compared with examples 13 and 15, the content of alkaline earth metal oxide (such as CaO) in the glass is further increased, and the content of ZnO is reduced, wherein CsNO is higher than that of CsNO3After 10h of exchange in the molten salt at 500 ℃, the Cs ion exchange layer depth was reduced to 24 μm.
Example 17 in comparison with examples 13 and 15 to 16, the content of ZnO in the glass was increased and the content of alkaline earth metal oxide in the glass was decreased, and CsNO was used3After exchanging in the molten salt at 500 ℃ for 10h, the depth of the Cs ion exchange layer is increased to 80 μm.
Example 18 compared to example 17, the use of an alkaline earth metal oxide partially in place of ZnO reduced the Cs ion exchange layer depth to 56 μm.
Examples 19-20 compared to example 13, Na was used2O in place of K2O (or similarly using NaX instead of KX, or further cross-over substitutions, e.g. NaX instead of K2O, etc.) will reduce the Cs ion exchange layer depth. The main reason is that the difference between the ionic radii of Na and Cs is larger than that between K and CsLarge, resulting in increased difficulty of ion exchange.
The examples in table 1 fully illustrate that the depth of the Cs ion exchange layer in the glass can be effectively controlled by adjusting the composition of the glass. Further, according to the characteristics and common knowledge of ion exchange, the relative concentration of Cs ions and K ions (or Na ions) in the molten salt is further adjusted, and the depth of a Cs exchange layer in the glass can be regulated and controlled.
The invention prepares halide nanocrystalline on the surface of glass through ion exchange. CsPbX having luminescence characteristic in visible light band other than the above3Other types of nanocrystals Cs4PbX by ion exchange in addition to nanocrystals6Halide nanocrystals such as CsX, KX, etc. can also be present in the surface layer of the glass after ion exchange, and the content thereof is closely related to the degree of ion exchange. In examples 1 to 20, CsPbX having luminescence characteristics and having a Cs ion distribution in the surface layer of glass was adjusted by adjusting the glass composition and the ion exchange temperature and time3The composition and distribution of the nanocrystalline are regulated and controlled. The present invention further illustrates the regulation of the Cs ion distribution and the Cs ion distribution by the ion exchange process conditions on the halide nanocrystal species and their relative content in the surface layer of the ion exchange glass in combination with the examples 21-26 in Table 2. It can be seen from the foregoing examples 1-20 that the similar effects can be obtained by adjusting the glass composition, and further description of the examples is omitted here. To more clearly illustrate the effect of ion exchange on halide nanocrystals in the surface layer of glass, examples 21-26 used the same glass composition, i.e., SiO2 18.1％，Al2O37.6％，B2O3 31.4％，ZnO 10.5％，CaO 1.9％，PbO 6.7％，Na2O8.6 percent and KBr 15.2 percent; the glass with the composition is uniformly mixed and then melted for 20min at 1230 ℃, and then is rapidly cooled, formed and annealed to obtain the completely transparent glass. The molten salt is CsNO3Molten salt or CsNO3/KNO3And (4) mixing the molten salt. In examples 21 to 26, the ion-exchanged glasses produced luminescence in the green band, and it was determined that CsPbBr was formed in the ion-exchanged glasses in combination with the glass composition3And (4) nanocrystals. Table 2, compositions of glasses of examples 21 to 26,Molten salt for exchange, ion exchange conditions, halide nanocrystalline phase species, and CsPbBr therein3Variation range of central wavelength of luminescence peak of nanocrystal
Figure BDA0003419417650000111
Figure BDA0003419417650000121
Example 21
This example uses pure CsNO3Fused salt, exchange at 460 ℃ for 2,4,6,8h, or after 480 ℃/2,4,6h, ion exchanged glass has tunable absorption (fig. 12, fig. 13) and luminescence (fig. 14, fig. 15) in the visible band. In the absorption spectrum, the glass after ion exchange has absorption in a visible light wave band, and the peak shoulder positions are respectively located at 490nm (460 ℃/2h), 494nm (460 ℃/4h), 497nm (460 ℃/6h), 500nm (460 ℃/8h), 501nm (480 ℃/2h), 504nm (480 ℃/4h) and 505nm (480 ℃/6 h); under the excitation of blue light, the ion exchange samples all generate luminescence in a visible light wave band, and the luminescence peak is adjustable within the range of 507-523nm along with the extension of the exchange time or the increase of the exchange temperature. FIGS. 16 and 17 are XRD patterns of the samples after 460 deg.C/2, 4,6,8h and 480 deg.C/2, 4,6h ion exchange treatments, respectively. Cs is observed in the graph as the exchange time is prolonged after 460 ℃ and 480 ℃ ion exchange4PbBr6The sharp diffraction peak of the nanocrystal (JCPDS card number: 73-2478) shows that the halide nanocrystal formed in the glass is mainly Cs4PbBr6A nanocrystal; however, the glass has adjustable absorption and luminescence in the visible light wave band, which shows that CsPbBr also exists in the glass3And (4) nanocrystals. CsAlSiO was also observed in the 480 ℃ ion-exchanged glass for a long time4(JCPDS card number: 47-471) crystal precipitation.
Example 22
The difference between this example and example 21 is that CsNO in the molten salt used3/KNO3In a ratio of 3: 1. FIGS. 18 and 19 are AP and 460 deg.C/2, 4,6h, 480And (3) an absorption spectrum of the sample after ion exchange treatment at the temperature of 2,4 and 6 hours. The absorption cut-off edge of the sample gradually red shifts and more obvious shoulder peaks appear along with the increase of the ion exchange temperature and the extension of the exchange time, and meanwhile, the absorption intensity of the shoulder peaks is obviously enhanced and moves to the long wavelength direction; the acromion positions are 497nm (460 ℃/2h), 499nm (460 ℃/4h), 502nm (460 ℃/6h), 505nm (480 ℃/2h), 508nm (480 ℃/4h) and 508nm (480 ℃/6h) respectively. FIGS. 20 and 21 are graphs of luminescence spectra of samples after AP and 460 deg.C/2, 4,6h, 480 deg.C/2, 4,6h ion exchange treatment. After ion exchange, the luminescence peak of the sample gradually changes from a broad peak to a narrow peak and moves to the long wavelength direction along with the increase of the exchange temperature and the time extension. The luminescence peak position is adjustable within the range of 510-525 nm. FIGS. 22 and 23 are XRD patterns of samples after 460 deg.C/2, 4,6h and 480 deg.C/2, 4,6h ion exchange treatments. After 460 ℃ and 480 ℃ ion exchange, the result from Cs was observed as the exchange time was extended4PbBr6The sharp diffraction peak of the crystal (JCPDS card number: 73-2478) and the diffraction peak is gradually strengthened, which shows that the crystallization amount is gradually increased; however, the glass has adjustable absorption and luminescence in the visible light wave band, which shows that CsPbBr also exists in the glass3And (4) nanocrystals.
Example 23
The difference between this example and examples 21 to 22 is that CsNO in the molten salt used3/KNO3In a ratio of 5: 3. FIGS. 24 and 25 are absorption spectra of samples after AP and 460 ℃/2,4,6h, 480 ℃/2,4,6h ion exchange treatment. The absorption cut-off edge of the sample gradually red shifts and more obvious shoulder appears along with the increase of the ion exchange temperature and the extension of the exchange time, and meanwhile, the absorption intensity of the shoulder is obviously enhanced and moves to the long wavelength direction. The peak shoulder positions are respectively located at 496nm (460 ℃/2h), 500nm (460 ℃/4h), 504nm (460 ℃/6h), 509nm (480 ℃/2h), 509nm (480 ℃/4h) and 509nm (480 ℃/6 h). FIGS. 26 and 27 are graphs of luminescence spectra of samples after AP and 460 deg.C/2, 4,6h, 480 deg.C/2, 4,6h ion exchange treatment. After ion exchange, the luminescence peak of the sample gradually changes from a broad peak to a narrow peak and moves to the long wavelength direction along with the increase of the exchange temperature and the time extension. The luminescence peak position is adjustable within the range of 512-524 nm. FIG. 28 shows ion exchange sites at 460 ℃/4,6h and 480 ℃/2,4,6hXRD pattern of the treated sample. After 460 ℃ and 480 ℃ ion exchange, the result from Cs was observed as the exchange time was extended4PbBr6The crystal (JCPDS card number: 73-2478) has sharp diffraction peak, but CsPbBr can be observed at the same time3The weak diffraction peak of the (JCPDS card number: 75-412) crystal shows that the composition of the crystal precipitated after ion exchange changes along with the decrease of the concentration of Cs ions in the molten salt.
Example 24
The difference between this example and examples 21 to 23 is that CsNO in the molten salt used3/KNO3In a ratio of 1: 1. FIGS. 29 and 30 are absorption spectra of samples after AP and 460 ℃/2,4,6h, 480 ℃/2,4,6h ion exchange treatment. The absorption cut-off edge of the sample gradually red shifts with the rising of the ion exchange temperature and the prolonging of the exchange time, and a more obvious peak shoulder appears, and meanwhile, the absorption intensity of the peak shoulder is obviously enhanced and moves to the long wavelength direction. The acromion positions are respectively 502nm (460 ℃/2h), 505nm (460 ℃/4h), 507nm (460 ℃/6h), 509nm (480 ℃/2h), 509nm (480 ℃/4h) and 510nm (480 ℃/6 h). FIGS. 31 and 32 are graphs of luminescence spectra of samples after AP and 460 deg.C/2, 4,6h, 480 deg.C/2, 4,6h ion exchange treatment. After ion exchange, the luminescence peak of the sample gradually changes from a broad peak to a narrow peak and moves to the long wavelength direction along with the increase of the exchange temperature and the time extension. The luminescence peak position is adjustable within the range of 514-525 nm. FIGS. 33 and 34 are XRD patterns for samples after 460 deg.C/2, 4,6h and 480 deg.C/2, 4,6h ion exchange treatments. After 460 ℃ and 480 ℃ ion exchange, it was observed that the product from CsPbBr was observed as the exchange time was prolonged3(JCPDS card number: 75-412) sharp diffraction peaks of the crystals.
Example 25
The difference between this example and examples 21 to 24 is that CsNO in the molten salt used3/KNO3In a ratio of 3: 5. FIGS. 35 and 36 are absorption spectra of samples after AP and 460 ℃/2,4,6h, 480 ℃/2,4,6h ion exchange treatment. The absorption cut-off edge of the sample gradually red shifts and a more obvious peak shoulder appears along with the increase of the ion exchange temperature and the extension of the exchange time, and meanwhile, the absorption intensity of the shoulder peak is obviously enhanced and moves to the long wavelength direction. The peak shoulder positions are respectively located at 507nm (46)0 ℃/4h), 510nm (460 ℃/6h), 510nm (480 ℃/2h), 510nm (480 ℃/4h), 511nm (480 ℃/6 h). FIGS. 37 and 38 are graphs of luminescence spectra of samples after AP and 460 deg.C/2, 4,6h, 480 deg.C/2, 4,6h ion exchange treatment. After ion exchange, the luminescence peak of the sample gradually changes from a broad peak to a narrow peak and moves to the long wavelength direction along with the increase of the exchange temperature and the time extension. The luminescence peak position is adjustable within the range of 514-521 nm. However, when the exchange temperature is 480 ℃, the narrow luminescence peak of the cesium-lead halide nanocrystalline is gradually weakened along with the extension of the exchange time, which is probably caused by the reduction of the luminescence efficiency due to the increase of the growth defects of the cesium-lead halide perovskite nanocrystalline particles. FIG. 39 is an XRD pattern of the samples after 460 deg.C/6 h and 480 deg.C/4, 6h ion exchange treatment. After 460 ℃ and 480 ℃ ion exchange, it can be observed that the ion exchange is derived from CsPbBr3(JCPDS card number: 75-412) sharp diffraction peaks of the crystals. However, as the ion exchange temperature increased and the time extended, a diffraction peak of KBr (JCPDS card number: 36-1471) crystals was observed, indicating that the K ion concentration promoted the crystallization of KBr as the Cs ion concentration in the molten salt decreased.
Example 26
The difference between this example and examples 21 to 25 is that CsNO in the molten salt used3/KNO3In a ratio of 1: 3. FIG. 40 is the absorption spectrum of the sample after the ion exchange treatment of AP and 460 ℃/4h, 480 ℃/4,6 h. The absorption cut-off edge of the sample gradually red shifts with the rising of the ion exchange temperature and the prolonging of the exchange time, and a more obvious peak shoulder appears, and meanwhile, the absorption intensity of the peak shoulder is obviously enhanced and moves to the long wavelength direction. The acromion positions are respectively 505nm (460 ℃/4h), 510nm (480 ℃/4h) and 511nm (480 ℃/6 h). FIG. 41 is a graph of luminescence spectra of samples after AP and 460 deg.C/4 h, 480 deg.C/4, 6h ion exchange treatment. After ion exchange, the luminescence peak of the sample gradually changes from a broad peak to a narrow peak and moves to the long wavelength direction along with the increase of the exchange temperature and the time extension. The luminescence peak position is adjustable within the range of 515-519 nm. However, when the exchange temperature is 480 ℃, the narrow luminescence peak of the cesium-lead halide nanocrystalline is gradually weakened along with the extension of the exchange time, which is probably caused by the reduction of the luminescence efficiency due to the increase of the growth defects of the cesium-lead halide perovskite nanocrystalline particles. FIG. 42 is an XRD pattern of samples after 460 deg.C/6 h and 480 deg.C/4, 6h ion exchange treatment.Sharp diffraction peaks from KBr (JCPDS card number: 36-1471) crystals were observed after 460 ℃ and 480 ℃ ion exchange. And as the ion exchange temperature increases and time is prolonged, the diffraction peak increases.
The above-described embodiments merely illustrate the embodiments of the present invention, but the present invention is not limited to the above-described embodiments. The present invention can be modified and improved by those skilled in the art without departing from the spirit of the present invention, and these are within the scope of the present invention.

Claims (10)

1. The halide nanocrystalline dispersion glass is characterized in that the surface layer of the dispersion glass is a Cs ion exchange layer, the halide nanocrystals are distributed in the Cs ion exchange layer, and the halide nanocrystals comprise CsPbX3、Cs4PbX6CsX or KX, wherein X is one or the combination of more than two of Cl, Br and I.
2. The halide nanocrystalline dispersed glass according to claim 1, wherein the ion exchange layer has a depth of 0 to 80 μm.
3. The halide nanocrystalline dispersed glass according to claim 1, wherein the network former of the glass is SiO2、B2O3、GeO2、TeO2Or P2O5One or a combination of two or more of them.
4. The halide nanocrystalline dispersed glass according to claim 1, wherein the composition of the glass comprises, in mole percent: 1-8% of PbO and 3-16% of AX, wherein A is any one or the combination of more than two of Li, Na or K, and X is one or the combination of more than two of Cl, Br or I.
5. The halide nanocrystal dispersed glass of claim 1, wherein the halide nanocrystal CsPbX3The specific kind of (b) corresponds to the halogen element contained in the glass.
6. The halide nanocrystalline dispersed glass according to claim 1, wherein the Cs ion exchange layer is an exchange between alkali metal cations in the glass and cesium ions in the cesium-containing molten salt; the cesium-containing molten salt is Cs molten salt, Cs/K mixed molten salt, Cs/Na mixed molten salt or Cs/K/Na mixed molten salt.
7. The halide nanocrystalline dispersed glass according to claim 1, wherein the ion exchange temperature is 420 to 510 ℃.
8. The halide nanocrystal dispersed glass of claim 6, wherein the nanocrystals are Cs when the molar ratio of Cs/K in the molten salt is greater than or equal to 14PbX6And/or CsPbX3A nanocrystal; when the molar ratio of Cs/K in the molten salt is less than 1, the nanocrystal is CsPbX3Nanocrystals and KX nanocrystals.
9. The halide nanocrystal dispersed glass of claim 1, wherein CsPbX is present in the dispersed glass3The absorption band and the luminescence band of the nanocrystal can be regulated and controlled within the range of 450-700 nm.
10. Use of the halide nanocrystal dispersed glass of claim 1 in the field of lighting assemblies, light source devices, spectral conversion devices, or light emitting pointing devices.
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